U.S. patent application number 11/980536 was filed with the patent office on 2008-09-04 for process for preparing a hydrogenation catalysts.
This patent application is currently assigned to Archer-Daniels-Midland Company. Invention is credited to Ronald T. Sleeter.
Application Number | 20080214852 11/980536 |
Document ID | / |
Family ID | 37187835 |
Filed Date | 2008-09-04 |
United States Patent
Application |
20080214852 |
Kind Code |
A1 |
Sleeter; Ronald T. |
September 4, 2008 |
Process for preparing a hydrogenation catalysts
Abstract
Copper compositions that are useful as hydrogenation catalysts
are disclosed. In particular, the copper compounds are catalysts
for the selective hydrogenation of oils that contain unsaturated
fatty acyl components such as unsaturated vegetable oils. Methods
of preparing the copper compositions are also disclosed. Methods of
hydrogenating unsaturated compositions that contain at least two
sites of unsaturation using the hydrogenation catalysts, along with
products obtained from the hydrogenation reactions described herein
are also disclosed.
Inventors: |
Sleeter; Ronald T.;
(Decatur, IL) |
Correspondence
Address: |
STERNE, KESSLER, GOLDSTEIN & FOX P.L.L.C.
1100 NEW YORK AVENUE, N.W.
WASHINGTON
DC
20005
US
|
Assignee: |
Archer-Daniels-Midland
Company
Decatur
IL
|
Family ID: |
37187835 |
Appl. No.: |
11/980536 |
Filed: |
October 31, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11407193 |
Apr 20, 2006 |
|
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11980536 |
|
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60674707 |
Apr 26, 2005 |
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Current U.S.
Class: |
554/141 |
Current CPC
Class: |
C11C 3/126 20130101;
B01J 23/72 20130101 |
Class at
Publication: |
554/141 |
International
Class: |
C07C 51/36 20060101
C07C051/36 |
Claims
1-15. (canceled)
16. A process of preparing a hydrogenation catalyst comprising: (a)
preparing a mixture by contacting copper carbonate/copper hydroxide
material with a hydrogen peroxide solution, wherein said mixture is
maintained at temperatures from about -5.degree. C. to about
100.degree. C.; and (b) separating a solid material from said
mixture; wherein a hydrogen peroxide-treated copper
carbonate/copper hydroxide hydrogenation catalyst is prepared.
17. The process of claim 16, wherein said hydrogen peroxide
solution is about 1% to 90% hydrogen peroxide.
18. The process of claim 17, wherein said hydrogen peroxide
solution is about 40% to 60% hydrogen peroxide.
19. The process of claim 16, wherein said mixture is maintained at
temperatures from about -5.degree. C. to about 30.degree. C.
20. The process of claim 16, wherein separating said solid material
from said mixture comprises centrifugation, settling, decantation,
filtration, or any combination thereof.
21. The process of claim 16, further comprising slurry grinding the
solid material of step (b) with a hydrogen peroxide solution.
22. A hydrogenation catalyst made by the process of claim 16.
23. The catalyst of claim 22, wherein the catalyst is
unsupported.
24-38. (canceled)
39. A process of preparing a hydrogenation catalyst comprising: (a)
preparing a mixture by contacting a copper hydroxide material with
a hydrogen peroxide solution, wherein said mixture is maintained at
temperatures from about -5.degree. C. to about 100.degree. C.; and
(b) separating a solid comprising said catalyst, wherein a hydrogen
peroxide-treated copper hydroxide hydrogenation catalyst is
prepared.
40. The process of claim 39, wherein said hydrogen peroxide
solution is about 1% to about 90% hydrogen peroxide.
41. The process of claim 39, wherein said temperatures in step a)
are from about -5.degree. C. to about 30.degree. C.
42. The process of claim 39, further comprising heating the
hydrogen peroxide-treated copper hydroxide hydrogenation catalyst
in an oil in the absence of additional hydrogen.
43. A process of preparing a hydrogenation catalyst comprising
heating a copper carbonate/copper hydroxide material at a
temperature of not less than about 100.degree. C. until said
material is black in color, wherein a heat treated copper
carbonate/copper hydroxide hydrogenation catalyst is prepared.
44. The process of claim 43, comprising: (a) heating a copper
carbonate/copper hydroxide material at a temperature from about
100.degree. C. to about 320.degree. C., and (b) heating the
material of step a) at a temperature at least about 5.degree. C.
higher than the temperature in step a).
45. A process of preparing a hydrogenation catalyst comprising: (a)
heating a copper metal powder material at a temperature from about
50.degree. C. to about 500.degree. C.; and (b) subjecting said
copper powder from step a) to a process that disrupts agglomerates
and clumps, wherein a heat-treated copper powder hydrogenation
catalyst is prepared.
46. The process of claim 45, wherein said copper powder has an
average particle size of about 0.5 micron.
47. The process of claim 45, further comprising: c) subjecting the
product of step b) to a vacuum and/or drying step.
48. The process of claim 45, further comprising: c) heating the
product of step b) at a temperature from about 50.degree. C. to
about 500.degree. C.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/674,707, filed Apr. 26, 2005, which is
incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention is directed to copper catalysts useful
for hydrogenating unsaturated compositions, methods of preparing
the catalysts, methods of hydrogenating unsaturated compositions
and the hydrogenated products obtained therefrom.
[0004] 2. Background of the Invention
[0005] The hydrogenation of unsaturated substrates is a technology
widely used for obtaining products which can be used in various
fields, from the food industry to the field of plastic materials
and the like. Several methods are known for hydrogenation (a
chemical reduction by means of adding hydrogen across a double
bond), most of which use gaseous hydrogen in the presence of a
suitable catalyst. The latter normally comprises a transition
metal, usually a metal of group 10 of the periodic table, i.e., Ni,
Pd or Pt. If these are present as impurities in the hydrogenated
substrate, they can cause oxidation or toxicological problems in
the case of food. Hydrogenation catalysts based on other transition
metals having fewer drawbacks than those listed above are also
known, but these also have a lower catalytic activity.
[0006] Hydrogenation of plant oils removes or reduces the amount of
components in the oil responsible for offensive odors, poor taste
and poor stability. Thus, hydrogenation provides plant oils that
are useful as components for many nutritional products such as
nutraceuticals and food, and for food preparation such as frying
oils.
[0007] Soybean (i.e., Glycine max L. Merr.) seeds are recognized to
represent one of the most important oilseed crops presently being
grown in the world. Such seeds provide an excellent source of
vegetable oil. While soybean oil represents an important worldwide
food source, flavor and oxidative stability problems associated
with its customary fatty acid composition reduces its
attractiveness in some applications.
[0008] Oxidative stability relates to how easily components of an
oil oxidize which creates off-flavors in the oil, and is measured
by instrumental analysis such as Oil Stability Index or Accelerated
Oxygen Method (AOM). The degree of oxidative stability is rated as
the number of hours to reach a peroxide value of 100.
[0009] Soybean oil contains five different fatty acids (in the form
of fatty acid acylglycerol esters) as its major components. These
five fatty acids are: palmitic acid (C16:0) which averages about 11
percent by weight; stearic acid (C18:0) which averages about 4
percent by weight; oleic acid (C18:1) which averages about 20
percent by weight; linoleic acid (C18:2) which averages about 57
percent by weight; and linolenic acid (C18:3) which averages about
8 percent by weight of the total fatty acids. The stability problem
which influences the flavor of soybean oil has been attributed to
the oxidation of its fatty acids, and particularly to the oxidation
of the linolenic acid (C18:3) component.
[0010] Oxidized fatty acids decompose to form volatile
flavor-imparting compounds. The relative order of sensitivity to
oxidation is linolenic>linoleic>oleic>saturates. Linolenic
acid has been known to be the primary precursor for undesirable
odor and flavor development. Since commodity soybean oil currently
marketed today contains relatively high amounts of linolenic acid
(7-10%) compared to other food oils such as corn oil which has
about 1%, its use is constricted unless it has been hydrogenated.
As a general rule the linolenic acid content should be below 1-2%
in order to have the widest food application and to qualify for
rigorous use environments such as for frying oils.
[0011] Soybean oil suffers from a lack of stability for frying
applications due to its relatively high concentration of linolenic
acid of 7 to 10%. This causes the oil to oxidize rapidly and
generate off flavors and also causes early breakdown in the frying
applications, resulting in premature foaming and darkening. Frying
stability can be enhanced if the linolenic acid concentration can
be reduced.
[0012] To address the flavor and stability problems of soybean oil
due to the linolenic acid content, various processing approaches
have been proposed. Such processing of the soybean vegetable oil
includes: (1) minimizing the ability of the fatty acids to undergo
oxidation by adding metal chelating agents, antioxidants, or
packaging in the absence of oxygen; or (2) the elimination of the
endogenous linolenic acid by selective hydrogenation. These
approaches have not been entirely satisfactory. The additional
processing is expensive, time consuming, commonly ineffective, and
frequently generates undesirable by-products. While selective
hydrogenation to reduce the linolenic acid content may improve oil
stability somewhat, this also generates positional and geometric
isomers of the unsaturated fatty acids that are not present in the
natural soybean oil.
[0013] Hydrogenation can be used to improve performance attributes
by lowering the amount of linolenic and linoleic acids in the oil.
In this process the oil increases in saturated and trans fatty
acids, both undesirable when considering health implications. In
many instances, the increase in trans fatty acids is proportional
to the amount of linolenic acid in the starting oil.
[0014] Due to increased knowledge of the behavior of trans fats,
i.e. trans fatty acid esters, in the human body and concerns of
their contributing to coronary heart disease, it is recommended
that the intake of trans fats be reduced. Research has shown that
diets high in saturated fats increase low density lipoproteins,
which promote the deposition of cholesterol on blood vessels. More
recently, dietary consumption of foods high in trans fatty acids
have also been linked to a lowering of high density lipoprotein
relative to low density lipoprotein and to cause an increase in
inflammation. In the United States, food companies are required to
label the trans content of their products above a threshold level.
This has added impetus to lower the amount of trans fats in foods,
particularly foods relatively high in oil, such as fried foods,
including potato chips, etc. However, hydrogenation remains the
primary option to convert an unstable oil to a stable oil.
[0015] Thus, polyunsaturated oils are hydrogenated to reduce the
degree of unsaturation in the oil, prior to subsequent processing
to obtain secondary products, such as food grade oils, additives,
lubricants and the like. The content of linolenic acid (C18:3) in
the oil is reduced by hydrogenation to a more saturated oil,
containing increased amounts of the monoene (C18:1) and diene
(C18:2).
[0016] Reduction of the double bond content in polyunsaturated oils
is traditionally carried out by partial hydrogenation, catalyzed by
a transition metal catalyst. Various transition metals, such as
nickel, palladium and platinum have been used as hydrogenation
catalysts. Catalysts vary in degree of selectivity. The selectivity
referred to in this context is the ability of preferentially
reducing linolenic acid before linoleic acid and oleic acid.
Selectivity in this context also applies to the ability of a
catalyst to reduce by hydrogenating only to form monoenes, without
reducing to full saturation. Precious metal catalysts are generally
the most active and also the least selective. They typically
produce high amounts of saturated fatty acids for a minimal
reduction of linolenic acid. Nickel catalysts are more selective
and have a greater preference for reducing linolenic acid to
monoene while producing less saturates. However, copper-chromium
combination catalysts (i.e., copper chromite catalyst) have
hitherto been found to be the most selective for production of the
monoene. The hydrogenation of the polyunsaturated oils with copper
chromite can produce the corresponding monoene, with little or no
production of the saturated fatty acid.
[0017] Nickel catalyzed hydrogenation uses small amounts of
catalyst for relatively short periods of time to reduce the
linolenic acid content to the desired range, which is often 1.5%.
The oil may then additionally be winterized (chilled and cold
filtered) to remove any crystalline fractions. A problem with the
hydrogenation processes of today is that double bonds in fatty
acids can also isomerize to form trans fatty acids during
hydrogenation, many of which are rare in nature. Some of these are
trans fatty acids. When nickel catalysts are used, saturated and
trans fatty acids are produced in high amounts relative to the
desired amount of reduction of linolenic acid. This is because
nickel catalysts suffer from a lack of optimum selectivity. As a
result, the trans fatty acid content of oils hydrogenated with
nickel catalysts can be higher than 10%.
[0018] Hydrogenation conditions to minimize trans isomer formation
while reducing the oxidatively unstable species in edible oil, such
as the polyunsaturated acids linolenic and linoleic acid, are
currently being studied by many in the industry. Those catalysts
currently being examined are generally precious metal based, and
hydrogenation is carried out under extremely mild conditions, such
as low temperatures. However, to date this has only resulted in a
minimal decrease in trans fatty acid content in hydrogenated oils,
at the cost of increased saturated fatty acid content and the use
of very expensive catalysts.
[0019] Precious metal catalysts can be poisoned from various minor
components in oils. As a result activity is lost over time and
reaction conditions must be continually monitored and altered.
These catalysts may be employed in column reactors which require
emptying and recharging after the useful catalyst life has ended.
The catalyst then must be returned to the catalyst company for
credit and regeneration. All of this involves catalyst loss and
added cost for column recycling. As precious metal catalysts lose
activity and must be recovered, users of precious metal catalysts
are often required to purchase a large excess of precious metal to
form a "pool" or "kitty" of precious metal, so that the catalyst
producer can provide fresh catalyst as needed. As a result, the use
of precious metal catalysts is accompanied by a very large capital
investment in precious metals.
[0020] Selective hydrogenation for producing oils for frying
applications using copper chromite catalyst has been known since at
least the late 1960's. Vegetable oils have been selectively
hydrogenated to decrease the linolenic acid content without
increasing the saturated fatty acid content constant and only
minimally decreasing the linoleic acid content in soybean oil. The
trans content was of no concern in those days as this was prior to
the discovery of the detrimental effects of these isomers to human
health. Selectively hydrogenating soybean oils produced oil with
less than 2% linolenic acid and improved frying stability. However,
copper chromite has low catalytic activity and requires very long
reaction times. Thus reactor time is measured in hours, not in
minutes, adding to increased production costs over comparable
nickel catalyzed reactions.
[0021] Further, copper chromite suffers from the problem that
chromium is one of the components of the catalyst, and thus any
plant using this catalyst must handle the recycling and disposal of
chromium in a satisfactory manner. First, the catalyst must be
recovered from the oil after the hydrogenation reaction by suitable
means, such as by centrifugation or filtering. Traces of catalyst
remaining in the oil must be removed in a thorough manner, such as
filtering through bleaching earth. This removal generates
significant quantities of solid waste containing spent copper
chromite catalyst and would require shipment to a land fill or to a
possible reclamation facility. In addition, the finely powdered
catalyst containing chromium could pose a significant health risk
to workers operating the processes.
[0022] Filtered oil further requires washing with a suitable
solution of chelating agent to further recover chromium. This wash
water would require passage through expensive ion exchange resin
columns to reduce the chromium concentration in the water prior to
discharge in order to achieve allowable limits. Further, regulatory
permits to allow discharge of trace levels of chromium in waste
water must be obtained. In order to measure chromium released to
the environment, expensive analytical monitoring equipment and
trained operators would be required. Because the use of copper
chromite was not attractive for the above reasons, its commercial
use as a hydrogenation catalyst is obsolete.
[0023] Other copper based catalysts are known in the art. These
catalysts have the advantage of being non-chromium. However, they
still have the disadvantage of being no faster than copper chromite
in reaction time. Furthermore, some were fabricated on a support,
generally a molecular sieve, making them somewhat expensive to
make. In addition, high hydrogenation temperatures were required
(170 to 200.degree. C.). To prepare these catalysts, a support
material was slurried in a solution of copper (II) nitrate, and
sodium carbonate was added to precipitate copper (II) carbonate
onto the support. This preparation was then heated to 350.degree.
C. for two hours.
[0024] Genetic varieties of soybeans containing oil with low
linolenic acid required for frying have just begun to be
commercialized. The most recent variety to be commercialized has
utilized a traditional genetic breeding program for its
development. In general, oils produced from genetic varieties are
expensive alternatives to hydrogenated oils.
[0025] There is an evident need in the fats and oils industry for
an economical catalyst for soybean oil hydrogenation which
selectively reduces linolenic acid without generation of
significant levels of trans fatty acids or formation of saturated
fatty acids.
BRIEF SUMMARY OF THE INVENTION
[0026] The copper compositions disclosed herein are useful as
hydrogenation catalysts. In particular, the copper compositions are
catalysts for the selective hydrogenation of oils that contain
unsaturated fatty acyl components. The present invention is also
directed to a method of preparing the copper compositions that are
useful as hydrogenation catalysts. The present invention is further
directed to a method of hydrogenating compositions containing at
least two sites of unsaturation. The present invention is also
directed to the products obtained from the hydrogenation reactions
described herein.
DETAILED DESCRIPTION OF THE INVENTION
[0027] In embodiments of the invention, the present invention is
directed to processes of hydrogenating a composition containing at
least two sites of unsaturation. The processes comprise: a)
preparing a mixture by contacting the composition with a
hydrogenation catalyst comprising at least one of the following
materials: heat-treated copper metal, chemically and optionally
heat-treated copper hydroxide, heat or chemically treated copper
carbonate/copper hydroxide, and a malachite material; and b)
heating the mixture at a temperature from about 50.degree. C. to
about 250.degree. C. under a hydrogen atmosphere; where the
composition is hydrogenated.
[0028] In all aspects of the present invention, the temperature,
temperatures or ranges represent the temperature at which the step
is conducted. However, the temperature can be more than one
temperature in the given range because of fluctuations in
temperature during the step.
[0029] In an embodiment, the temperature for step b) can be any
temperature(s) from about 50.degree. C. to about 250.degree. C. In
other embodiments, the temperature is from about 100.degree. C. to
about 250.degree. C., or from about 100.degree. C. to about
200.degree. C., or from about 160.degree. C. to about 200.degree.
C., or from about 140.degree. C. to about 220.degree. C.
Illustratively the temperature is about 160.degree. C., about
180.degree. C., or about 200.degree. C.
[0030] The term "hydrogenation" is well-known in the art, and the
term "hydrogen atmosphere" is known to mean that the atmosphere in
contact with the unsaturated composition comprises hydrogen gas.
The pressure of hydrogen includes the range of about 5 psi to about
1000 psi. In embodiments of the invention, the value is from about
20 psi to about 150 psi, or from about 40 psi to about 80 psi.
[0031] The time for which the mixture is heated under a hydrogen
atmosphere is dependent, inter alia, upon the catalyst of the
invention that is used and the desired properties of the resulting
hydrogenated composition. For example, the time can range from
about 1 minute to about 48 hours (for example, about 30 minutes to
about 8 hours, or about 30 minutes to about 4 hours).
[0032] Suitable compositions for the present method include any
composition containing at least two sites of unsaturation. Such
compositions can comprise a single compound or mixtures of
compounds wherein at least one compound contains at least two sites
of unsaturation. The method described herein is useful for fully
hydrogenating or partially hydrogenating the composition. As such,
the terms "hydrogenation" or "hydrogenating" as used herein are
intended to include partial hydrogenation.
[0033] Polyunsaturated fatty acyl compositions comprise compounds
and mixtures that contain compounds of the following generic
structure:
##STR00001##
wherein R is a carbon chain from about 2 to about 23 carbons and
contains at least two sites of unsaturation; A can be a residue of
a monohydric alcohol, a diol, polyol, or glycerol, or a hydroxy,
alkoxy or aryloxy moiety. The above general structure includes the
following substructure:
##STR00002##
wherein R is as described above, and G.sup.1 and G.sup.2 are each
independently selected from the group consisting of hydrogen
and,
##STR00003##
wherein Z represents a carbon chain from about 2 to about 23
carbons in length, optionally having at least two sites of
unsaturation. This formula encompasses the fatty acid esters
commonly found in vegetable oils and polyunsaturated vegetable oils
such as palmitic acid (C16:0); stearic acid (C18:0); oleic acid
(C18:1); linoleic acid (C18:2); and linolenic acid (C18:3).
[0034] Preferably, the fatty acyl composition containing at least
two sites of unsaturation is a vegetable, animal or synthetic fat
or oil, or derivatives or mixtures thereof. References made herein
to "fatty acids" are intended to mean fatty acids in the form of
fatty acid esters in the fatty acyl composition, that is a
vegetable, animal or synthetic fat or oil, or derivatives or
mixtures thereof, unless the fatty acid is specifically referred to
as a "free fatty acid." In this context, it is preferred that the
fatty acid or derivative thereof is a triglyceride, diglyceride or
monoglyceride or alkyl ester containing a residue of the fatty
acid.
[0035] References to levels of "fatty acids" in oils refer to the
level of fatty acid chains in the form of esters such as
glycerides. For example, a fatty acyl containing composition
comprising one or more polyunsaturated (i.e. two or more sites of
unsaturation) vegetable fatty acid(s) or derivatives or mixtures
thereof can include the fatty acids contained in oils in the form
of fatty acid esters.
[0036] In the generic structure above, when A is a residue of
glycerol, then the fatty acyl composition can comprise a
triglyceride, diglyceride and/or monoglyceride of a fatty acid
(i.e., glycerol alkanoates), and mixtures thereof. Such a
diglyceride or triglyceride will have two or three fatty acid
chains, respectively, wherein at least one of the chains has at
least two sites of unsaturation. More preferred mono-, di- and
triglycerides include glycerides of vegetable oil fatty acids. Most
preferably, such glycerides are naturally occurring in a vegetable
oil starting material.
[0037] In this preferred embodiment, the fatty acyl containing
composition is an edible oil. Preferred edible oils include
vegetable oils. Suitable vegetable oils include but are not limited
to: soybean oil, linseed oil, sunflower oil, canola oil, rapeseed
oil, cottonseed oil, peanut oil, safflower oil, derivatives and
conjugated derivatives of said oils, and mixtures thereof. These
oils are known as polyunsaturated vegetable oils. Most preferably,
the oil is soybean oil.
[0038] The present invention can be used to prepare oils low in
linolenic acid and lower in trans fatty acids than partially
hydrogenated oils prepared by conventional processes, such as with
nickel catalysts. The oils of the invention have good oxidative
stability due to the lowered content of linolenic acid.
[0039] Illustrative applications for use these oils include, but
are not limited to food and beverages, animal feed, technical
applications, nutritional supplements, beverages, cosmetics and
personal care products, and pharmaceuticals/nutraceuticals.
[0040] Illustrative food applications include frying fats and oils,
margarine oil, spread oil, bakery fats, frozen dough, cookies with
oil, cream cakes (foam cakes), yeast-raised cakes, bread products
(bread, buns, rolls), fried bread (with antioxidants),
confectionary products, icings, dairy products, cheese products,
pasta products, shortening, fat mixtures, emulsions, spray oils,
dressings, milk, non dairy protein powders, soups, dressings,
meats, gravies, canned meats, meat analogues, bread improvers,
beverages, energy drinks, snacks, desserts, ice cream and bars,
colors, flavor mixes, emulsifier mixes, baby food, frozen foods
fat, spray oil for bakery applications; releasing agent oil for
pans, belts, molds, and the like; incorporation into emulsions such
as sauces, creams, mayonnaise, toppings, yogurts, microwave popcorn
fat, and antioxidants.
[0041] Illustrative feed applications include sources of high
nutritional value in feed for, for example, fish, shrimp, calves
(as milk replacer), pigs, sows, piglets, companion animals, pets,
mink, and poultry.
[0042] In addition, oils of the invention can be used as a starting
material for derived processes and products, such as feedstock for
lipid modifications such as fractionation and chemical or enzymatic
transesterification or interesterification reactions to prepare
useful triacylglycerols, diacylglycerols, monoacylglycerols, esters
and waxes. The oils of the invention can also be blended with other
oils or fats to provide a blend having desired characteristics.
[0043] Derivatives of these oils include genetically modified oils.
One desired trait of genetically modified oils is the lower content
of linolenic acid compared to natural oils. Some low level
varieties have linolenic acid levels as low as about 1.2 to about
1.6%. In natural varieties, the level of linolenic acid is
generally about 7-10%. Low linolenic acid varieties can benefit
substantially by the hydrogenation method of the present invention
especially when the level of linolenic acid is above about 2%, but
below the usual amount contained in the corresponding natural
variety. The present method will yield a hydrogenated or partially
hydrogenated vegetable oil that contains conjugated linolenic
acid(s) (CLA), which are not present in the low-level
varieties.
[0044] When applied to a vegetable oil the present method of
hydrogenation advantageously yields a hydrogenated or partially
hydrogenated vegetable oil with desirable characteristics for use
where liquid oils are needed, such as in foods and food
preparation. The present method produces vegetable oils having a
linolenic content of no greater than about 5%. The same product
will also have a conjugated linolenic acid content of no greater
than about 1% and a trans fatty acid content of no greater than
about 10%. More preferred vegetable oil products of the present
method have a linolenic acid content of no greater than about 3%,
and most preferably 1%. These more preferred vegetable oils can
also have a trans fatty acid content of no greater than about 8%,
and most preferably no greater than about 3% as well as a
conjugated linolenic acid content no greater than about 1%.
[0045] Copper catalysts of the invention include heat-treated
copper metal, chemically and optionally heat-treated copper
hydroxide, and heat or chemically treated (e.g., hydrogen
peroxide-treated) copper carbonate/copper hydroxide (also referred
to as basic copper carbonate) compositions. It has been found that
the above copper compounds in their neat condition do not catalyze
the hydrogenation described herein to an appreciable degree, if at
all, and that these compounds can be made more catalytic by
employing the methods of preparing a catalyst described herein. In
another embodiment, a hydrogenation catalyst used in the
hydrogenation methods of the invention comprises a malachite
material (including natural malachite mineral and synthetically
prepared malachite (e.g., a precipitated malachite)).
[0046] In various embodiments of the invention, the catalysts used
in the hydrogenation methods of the invention (e.g., heat-treated
copper powder, heat-treated copper carbonate/copper hydroxide,
chemically treated copper carbonate/copper hydroxide, chemically
treated copper hydroxide, or malachite material) are unsupported
catalysts.
[0047] A copper metal powder material can be made a useful
hydrogenation catalyst when treated as described herein. A
representative copper metal powder can be obtained from Umicore
Canada (Fort Saskatchewan, Canada). Preferably, these copper
powders are high-purity, non-agglomerated, spheroidal products that
are also used in electronics applications, such as termination
pastes, inner electrode inks, and conductive traces. Four grades of
copper powder can be obtained from this manufacturer: UCP 500, UCP
1000, UCP 2000, and UPC 4000. They are characterized by the
manufacturer as having the following tap density (grams/cubic
centimeter), respectively: 3.6; 3.5; 3.6; and 4.8. In addition,
they are characterized by the manufacturer as having the following
surface areas (square meters/gram), respectively: 1.0; 0.8; 0.6;
and 0.4 and particle sizes (microns), respectively; 0.5; 1.0; 2.0;
and 4.0.
[0048] In particular, a heat-treated copper metal can be used in
the hydrogenation or partial hydrogenation of an unsaturated fatty
acyl compound using the process described above. Most preferably,
such a material comprises or consists essentially of a heat treated
copper metal hydrogenation catalyst having a particle size of about
0.5 microns. The heat treatment for this particular catalyst
comprises heating the copper metal powder at a temperature from
about 50.degree. C. to about 500.degree. C. More preferably the
temperature is from about 150.degree. C. to about 400.degree. C.,
and most preferably the temperature is from about 200.degree. C. to
about 350.degree. C. It is also preferred that the copper powder
material is heated in the presence of oxygen. Oxygen may be present
during the heat treatment by allowing ambient air or more purified
O.sub.2 to contact the copper powder material.
[0049] This catalyst is prepared by starting with a copper metal
powder as described above. This material is then heated as
described above, and then the material is preferably subjected to a
process that produces a powder of substantially uniform
consistency. The term "substantially uniform consistency" means a
powder material that is essentially free of agglomerated material
or clumps. During the heat treatment, agglomeration or clumping of
the copper powder may occur. It has been found that the catalytic
activity of the copper metal powder is improved if the agglomerates
or clumps are disrupted to form a powder material of substantially
uniform consistency. A heat treated copper metal powder
hydrogenation catalyst can comprise agglomerates or clumps but it
is preferred that the material is essentially free of them.
[0050] Any method of disrupting the agglomerates or clumps is
envisioned. Preferably, the material is tumbled, deagglomerated,
ground, stirred or slurried (with or without grinding) to disrupt
the agglomerates or clumps. Preferably, after disrupting the
agglomerates or clumps, the material can be heated again as
described above and/or the material can then be dried by vacuum,
heating or any other drying method known in the art.
[0051] A copper metal powder prepared as described above is a
useful hydrogenation catalyst especially for producing hydrogenated
vegetable oils as food ingredients or for food production. Using
the method described herein, such copper metal hydrogenation
catalysts preferably yield hydrogenated vegetable oils containing
the following ratios of fatty acids: C18:2/C18:0 above about 11.0;
C18:2/C18:1 no greater than about 2; C18:3/C18:0 no greater than
about 1. The process preferably yields a hydrogenated oil that
further comprises a trans fatty acid content of no greater than
about 8% depending on the content of linolenic acid in the starting
soybean oil.
[0052] All fatty acid ratios as described herein were derived by
determining the fatty acid profile of starting oils and
hydrogenated oil by gas chromatography (GC) according to AOCS
methods. Values for C18:0 were reported directly from
chromatography, values for C18:1 and C18:2 were obtained by summing
the contents of cis and trans isomers of C18:1 and C18:2 fatty
acids, respectively. Reactions were monitored by refractive index
(RI) and where fatty acid profiles are reported from this data it
was obtained by correlating these RI values to published data
containing both RI and GC data.
[0053] A copper carbonate/copper hydroxide material can be made to
be a useful hydrogenation catalyst when treated as described
herein. A copper carbonate/copper hydroxide material comprises
copper carbonate and copper hydroxide and can be described as basic
copper carbonate. Basic copper carbonate is a product of commerce
and contains about 50+% copper carbonate, with the remainder
consisting essentially of copper hydroxide. A representative
material can be obtained from World Metal, LLC (Sugar Land, Tex.,
USA). The density can range from about 500 to about 2000 kg/cubic
meter. The material is basic in character and insoluble in water.
As received from the manufacturer, the material can be green in
color. However, supplies often vary in shades of color and density
(darker green or olive, and heavier, lighter or fluffier)
reflecting variations in raw materials and manufacturing
procedures. Despite variations in the physical appearance of the
material, the amount of contained copper metal remains essentially
constant.
[0054] A heat or chemically treated copper carbonate/copper
hydroxide material can be used in the hydrogenation or partial
hydrogenation of an unsaturated fatty acyl compound using the
process described above. Such a material comprises or consists
essentially of a heat or chemically treated copper carbonate/copper
hydroxide hydrogenation catalyst.
[0055] The heat treatment for the copper carbonate/copper hydroxide
hydrogenation catalyst comprises heating a copper carbonate/copper
hydroxide material as described above to a temperature of not less
than about 100.degree. C. until the material is black in color, and
a hydrogenation catalyst is prepared. In a preferred embodiment,
the method of preparing a copper carbonate/copper hydroxide
hydrogenation catalyst comprises, a) heating a copper
carbonate/copper hydroxide material at a temperature no greater
than about 320.degree. C. (e.g., at a temperature from about
100.degree. C. to about 320.degree. C.), and b) heating the
material of step a) at a temperature at least about 5.degree. C.
higher than the temperature in step a). Thus, in step a) the
material is heated and then in step b), the temperature is
increased such that the material is then heated at a temperature at
least about 5.degree. C. higher than the temperature in step a). At
the end of this process, the catalyst will be black in color.
[0056] Most preferably, the method comprises three steps, a)
heating a copper carbonate/copper hydroxide material at a
temperature no greater than about 320.degree. C. for a first period
of time, b) disrupting any agglomeration or clumps in the material
possibly formed during heating, and c) heating the material of the
prior disrupting step at a temperature at least about 5.degree. C.
higher than the temperature in step a) for a second period of
time.
[0057] Preferably, the first period of time is not greater than
about 30 minutes, and the second period of time is a period of time
sufficient to produce a hydrogenation catalyst. Specifically, the
second period of time will be long enough to yield a catalyst that
is black in color. This second period of time is preferably from
about 1 minute to about 2 hours. More preferably, the second period
of time is from about 5 minutes to about 1 hour. Most preferably,
the second period of time is from about 10 minutes to about 25
minutes.
[0058] In any embodiment, the preparation of this catalyst can also
include a step of disrupting agglomerates or clumps during the
heating. Methods of disrupting agglomerates and clumps have been
described above. After conducting a process of disrupting the
agglomerates and clumps, it is preferred that the material has
substantially uniform consistency.
[0059] It is also preferred that the copper carbonate/copper
hydroxide material is heated in the presence of oxygen. Oxygen may
be present during the heat treatment by allowing ambient air or
more purified O.sub.2 to contact the copper powder material.
[0060] The copper carbonate/copper hydroxide hydrogenation catalyst
as described above is useful for producing hydrogenated vegetable
oils as food ingredients or for food production. Using the method
described herein, such copper carbonate/copper hydroxide
hydrogenation catalysts preferably yield hydrogenated vegetable
oils containing the following ratios of fatty acids respectively:
Illustrative Oil 1) 18:2/18:0 above about 11.0; 18:2/18:1 no
greater than about 2.2; 18:3/18:0 no greater than about 1.7; and
Illustrative Oil 2) 18:2/18:0 above about 11.0; 18:2/18:1 no
greater than about 2.2; 18:3/18:0 no greater than about 1. The
above oils preferably further comprise a trans fatty acid content
of no greater than about 8%.
[0061] In another embodiment of the invention, a catalyst
comprising a chemically treated copper carbonate/copper hydroxide
material can be used in hydrogenation or partial hydrogenation
using the process described above. By the term "chemically treated
copper carbonate/copper hydroxide material," it is meant that the
copper carbonate/copper hydroxide material is contacted with a
reagent to improve its ability to catalyze a hydrogenation
reaction.
[0062] In an embodiment, the copper carbonate/copper hydroxide
material is chemically treated with a hydrogen peroxide solution.
Thus, in this embodiment, a chemically treated copper
carbonate/copper hydroxide is prepared by a) preparing a mixture by
contacting copper carbonate/copper hydroxide material with a
hydrogen peroxide solution, wherein said mixture is maintained at
temperatures from about -5.degree. C. to about 100.degree. C.; and
b) separating a solid material from said mixture; wherein a
hydrogen peroxide treated copper carbonate/copper hydroxide
hydrogenation catalyst is prepared.
[0063] The hydrogen peroxide can be in the form of an aqueous
solution. Concentrations of aqueous hydrogen peroxide can range
from about 1% to about 90% hydrogen peroxide. In embodiments of the
invention, the concentration is from about 40% to about 60%, or
from about 45% to about 55%. In yet another embodiment, the
concentration is about 50% as supplied commercially.
[0064] As mentioned above, the mixture is maintained at
temperatures from about -5.degree. C. to about 100.degree. C. In an
embodiment, the mixture is maintained at temperatures from about
-5.degree. C. to about 30.degree. C.
[0065] The preparation of this catalyst can also include disrupting
agglomerates or clumps in the material. Agglomerates or clumps in
the material can be disrupted before and/or after the solid
material is separated from the mixture (step b, above). Methods of
disrupting agglomerates and clumps are described above. In
embodiments of the invention, agglomerates or clumps in the
material are disrupted by grinding, preferably by slurry grinding
in an appropriate liquid. For example, the material can be slurry
ground in hydrogen peroxide, which can be the same or different
from, and at the same or different concentration of, the hydrogen
peroxide used in step a). After slurry grinding, the material can
be separated from the liquid phase by any method known in the art
such as filtering (e.g. vacuum filtering), decanting, centrifuging,
or any combination thereof. Optionally, the material can then be
dried by vacuum, heating or other drying method known in the
art.
[0066] In an embodiment, the hydrogen peroxide-treated copper
carbonate/copper hydroxide hydrogenation catalyst may be subjected
to one or more additional chemical treatments with a hydrogen
peroxide solution. The hydrogen peroxide-treated copper
carbonate/copper hydroxide hydrogenation catalyst may be subjected
to any of rinsing, filtering or drying prior to being subjected to
one or more additional chemical treatments with a hydrogen peroxide
solution.
[0067] The copper carbonate/copper hydroxide hydrogenation catalyst
as described above is useful for producing hydrogenated vegetable
oils as food ingredients or for food production. Using the method
described herein, such copper carbonate/copper hydroxide
hydrogenation catalysts preferably yield hydrogenated vegetable
oils containing the following ratios of fatty acids: Illustrative
Oil 1) C18:2/C18:0 above about 11.0; C18:2/C18:1 no greater than
about 2.2; C18:3/C18:0 no greater than about 1.7; Illustrative Oil
2) C18:2/C18:0 above about 12.0; C18:2/C18:1 no greater than about
2.1; C18:3/C18:0 no greater than about 1.6; Illustrative Oil 3)
C18:2/C18:0 above about 12.2; C18:2/C18:1 no greater than about
2.0; C18:3/C18:0 no greater than about 1.4; and Illustrative Oil 4)
C18:2/C18:0 above about 11.3; C18:2/C18:1 no greater than about
1.65; C18:3/C18:0 no greater than about 0.65. The above oils
preferably further comprise a trans fatty acid content of no
greater than about 8%.
[0068] In another embodiment of the invention, a catalyst
comprising or consisting essentially of a chemically treated copper
hydroxide material can be used in hydrogenation or partial
hydrogenation using the process described above. By the term
"chemically treated copper hydroxide material," it is meant that
the copper hydroxide material is contacted with a reagent to
improve its ability to catalyze a hydrogenation reaction.
[0069] In an embodiment, the copper hydroxide material is
chemically treated with a hydrogen peroxide solution. Thus, in this
embodiment, the chemical treatment of a material comprising or
consisting essentially of a copper hydroxide material comprises, a)
preparing a mixture by contacting a copper hydroxide material with
a hydrogen peroxide solution, wherein said mixture is maintained at
temperatures from about -5.degree. C. to about 100.degree. C.; and
b) separating a solid comprising said catalyst, wherein a hydrogen
peroxide treated copper hydroxide hydrogenation catalyst is
prepared.
[0070] The hydrogen peroxide can be in the form of an aqueous
solution. Concentrations of aqueous hydrogen peroxide can range
from about 1% to about 90% hydrogen peroxide. In embodiments of the
invention, the concentration is from about 40% to about 60%, or
about 45% to about 55%. In yet another embodiment, the
concentration is about 50% as supplied commercially.
[0071] The temperature(s) in step a) are preferably from about
0.degree. C. to about 100.degree. C. The material can be separated
from the liquid phase by any method known in the art such as
filtering (e.g. vacuum filtering), decanting, centrifuging, or any
combination thereof. Optionally, the material can then be dried by
vacuum, heating or other drying method known in the art.
[0072] The copper hydroxide hydrogenation catalyst can also be
prepared by contacting with hydrogen peroxide as described herein,
followed by separating from the hydrogen peroxide by the methods
described herein, drying by any known method in the art, and
subsequently being heated in an oil at a temperature above about
50.degree. C. Preferably, the temperature is from about 100.degree.
C. to about 250.degree. C. The oil can be any oil, but preferably
the oil is an edible oil such as a vegetable oil. The copper
hydroxide hydrogenation catalyst can be separated from the oil if,
for example, the oil in this step is not a composition to be
hydrogenated, and used to hydrogenate a composition comprising at
least two sites of unsaturation. Preferably, the catalyst is heated
until the color of the catalyst is black.
[0073] The chemically treated copper hydroxide hydrogenation
catalyst as described above is useful for producing hydrogenated
vegetable oils as food ingredients or for food production. Using
the method described herein, such copper hydroxide hydrogenation
catalysts preferably yield hydrogenated vegetable oils containing
the following ratios of fatty acids: Illustrative Oil 1)
C18:2/C18:0 above about 11.0; C18:2/C18:1 no greater than about
1.8; C18:3/C18:0 no greater than about 1.0; Illustrative Oil 2)
C18:2/C18:0 above about 11.5; C18:2/C18:1 no greater than about
1.7; C18:3/C18:0 no greater than about 0.55; and Illustrative Oil
3) C18:2/C18:0 above about 11.7; C18:2/C18:1 no greater than about
1.69; C18:3/C18:0 no greater than about 0.53. The above oils
preferably further comprise a trans fatty acid content of no
greater than about 10%. More preferably, the above oils further
comprise a trans fatty acid content of no greater than about
8%.
[0074] A hydrogenation catalyst comprising a malachite material can
also be used in the hydrogenation or partial hydrogenation of an
unsaturated fatty acyl compound using the process described above.
By "malachite material," it is meant a synthetic or natural
material containing malachite. Malachite (also referred to in
scientific literature as copper (II) carbonate hydroxide,
Cu.sub.2CO.sub.3(OH).sub.2, basic copper carbonate, or copper
carbonate/copper hydroxide) has CAS Registry Number 1319-53-5 with
the following structure:
##STR00004##
[0075] In an embodiment of the invention, the malachite material is
naturally occurring malachite mineral. Natural malachite can be
found in the oxidations zone of polymetallic deposits in ore
fields, and appear as radiate-fibrous, spheroidal, and sintered
aggregates with shell-like cleavage, silky luster, and a
characteristic green color in varicolored band due to diverse grain
sizes. Natural malachite can be purchased in clumps from rock
collectors, and may contain trace amounts of phosphorus, calcium,
strontium, zinc and manganese.
[0076] In another embodiment of the invention, the malachite
material is synthetically prepared malachite. The synthetically
prepared malachite can be prepared by any suitable method. For
example, the synthetically prepared malachite is a precipitated
malachite, i.e., malachite prepared by a precipitation method, such
as by precipitation of copper cations and carbonate anions. A
suitable method of preparation of precipitated malachite is
disclosed in H. Parekh and A. Hsu, "Preparation of synthetic
malachite. Reaction between cupric sulfate and sodium carbonate
solutions," Industrial & Engineering Chemistry Product Research
and Development 7(3): 222-6 (1968). Examples of the preparation of
precipitated malachite are described in Example 9, below.
[0077] In an embodiment, the hydrogenation catalyst comprising a
malachite material (e.g. as a naturally occurring mineral or
synthetically prepared by precipitation) is unsupported. That is,
an unsupported catalyst comprising a malachite material according
to the present invention can be used for hydrogenation of an
unsaturated composition, and particularly for a composition
containing at least two sites of unsaturation.
[0078] In embodiments of the invention, the malachite material can
be chemically treated, i.e. contacted with a reagent to improve its
ability to catalyze a hydrogenation reaction. In an embodiment, the
malachite material is chemically treated by contacting it with a
hydrogen peroxide solution. For example, the malachite material can
be chemically treated by a) contacting the malachite material with
a hydrogen peroxide solution to form a mixture, and maintaining the
mixture at about -5.degree. C. to about 100.degree. C. and b)
separating the treated material from the mixture. The conditions
for preparing the chemically treated malachite (e.g., concentration
of reagent(s), temperature, and separation technique(s)) include
those discussed for the chemically treated copper carbonate/copper
hydroxide catalyst, above.
[0079] A hydrogenation catalyst comprising a malachite material as
described above is useful for producing hydrogenated vegetable oils
as food ingredients or for food production. Such malachite material
hydrogenation catalysts (and particularly the unsupported synthetic
precipitated malachite catalyst) preferably yield hydrogenated
vegetable oils containing the following ratios of fatty acids:
C18:2/C18:0 above about 10; C18:2/C18:1 no greater than about 1.76;
C18:3/C18:0 no greater than about 0.61. In embodiments, the above
hydrogenated oils further comprise a trans fatty acid content of no
greater than about 8%.
[0080] Any of the catalysts of the present invention (i.e.,
heat-treated copper metal, chemically and optionally heat-treated
copper hydroxide, heat or chemically treated copper
carbonate/copper hydroxide, and a malachite material) can be
further treated prior to use in a hydrogenation reaction in order
to improve its ability to catalyze a hydrogenation reaction. The
catalysts are further treated by heating the catalysts in an oil in
the presence or absence of additional hydrogen. The further treated
catalysts are then recovered from the oil and can be used to
catalyze hydrogenation reactions as disclosed herein.
[0081] The oil that can be used in the further treatment of the
catalysts of the invention is not particularly limited, and can
include any vegetable oil, animal oil, butterfat, cocoa butter,
cocoa butter substitutes, illipe fat, kokum butter, milk fat,
mowrah fat, phulwara butter, sal fat, shea fat, borneo tallow,
lard, lanolin, beef tallow, mutton tallow, tallow, animal fat,
canola oil, castor oil, coconut oil, coriander oil, corn oil,
cottonseed oil, hazelnut oil, hempseed oil, jatropha oil, linseed
oil, mango kernel oil, meadowfoam oil, mustard oil, neat's foot
oil, olive oil, palm oil, palm kernel oil, peanut oil, rapeseed
oil, rice bran oil, safflower oil, sasanqua oil, shea butter,
soybean oil, sunflower seed oil, tall oil, tsubaki oil, tung oil,
marine oils, menhaden oil, candlefish oil, cod-liver oil, orange
roughy oil, pile herd oil, sardine oil, whale oils, herring oils,
triglyceride, diglyceride, monoglyceride, triolein palm olein, palm
stearin, palm kernel olein, palm kernel stearin, triglycerides of
medium chain fatty acids, and derivatives, conjugated derivatives,
genetically-modified derivatives and mixtures thereof.
[0082] The temperature and time for which the catalyst/oil mixture
is heated to further treat the catalyst is not particularly
limited. In embodiments of the invention, the temperature is from
about 100.degree. C. to about 200.degree. C., and the time ranges
from about 1 minute to about 120 minutes, typically about 15
minutes
[0083] The further treated catalysts of the invention are expected
to provide a lowered linolenic acid content and/or lowered trans
fatty acid formation in a hydrogenation reaction compared to
catalysts that are not further treated. Further treatment of a
copper hydroxide catalyst and the results of hydrogenation using
that catalyst is illustrated in Example 7, below.
[0084] The catalysts of the present invention can be reused or
recycled. Thus, the catalysts described herein can be used to
hydrogenate or partially hydrogenate subsequent compositions
comprising at least two sites of unsaturation. In one example of
this embodiment, following the step of heating a mixture comprising
a catalyst and a composition comprising at least two sites of
unsaturation under a hydrogen atmosphere, the solid material is
separated from the mixture.
[0085] Separation of the solid material from a hydrogenated oil can
be performed by any means, such as those described above for
separating a solid from a non-solid material, and at any convenient
processing temperature. Suitable methods include centrifugation,
settling, decantation, filtration (e.g., vacuum filtration),
contact with a filter aid, contact with a liquid or solid chelating
agent, addition of an activated adsorbent, or any combination
thereof. For example, vacuum filtration can be carried out using
filter aids, such as Celite 503 Diatomaceous Earth (World Minerals
Inc., Goleta, Calif.). Other separation methods include contact
with a liquid or solid chelating agent such as citric acid
solution, by addition of activated adsorbent such as activated
SorbsilR92 (INEOS Silicas Americas, LLC, Joliet, Ill.), and
filtering through a filter aid.
[0086] Subsequent to separation, the solid material can be
contacted with a composition containing at least two sites of
unsaturation to form a mixture, and this will then be heated at a
temperature from about 50.degree. C. to about 250.degree. C. under
a hydrogen atmosphere wherein said composition is hydrogenated.
This process can be repeated such that the solid material
comprising the hydrogenation catalyst is contacted with subsequent
compositions containing at least two sites of unsaturation and then
separated from the hydrogenated compositions, wherein the
hydrogenated compositions will have been hydrogenated using the
methods described herein.
EXAMPLES
Example 1
Hydrogenation Using Neat Powders
[0087] Neat powders as received from various chemical supply
companies were tested as hydrogenation catalysts without any
pretreatment.
[0088] Hydrogenation reaction: Soybean oil (Linolenic acid 7.1%,
trans fatty acid 0.2%, Conjugated linoleic acid 0.1%) was dewatered
under vacuum (ca. 0.5-2 torr) at 80-85.degree. C.; 600 grams of
dewatered soybean oil were charged into a 2 liter pressure reactor
(Parr Model 4542). Catalyst (nominally 0.1% copper as a percentage
of oil used in a given reaction) was added, and the vessel was
sealed. The reaction mixture was heated to 160.degree. C. under a
hydrogen atmosphere of 60 psi with a slight hydrogen gas purge
through a fritted disk in the bottom of the vessel. The results are
given below in Table 1:
TABLE-US-00001 TABLE 1 Final Linolenic Final trans Reaction acid
content fatty acid Final CLA* Catalyst time (%) content (%) content
(%) Cu(OAc).sub.2 No Reaction Cu(NO.sub.3).sub.2 No Reaction
CuCl.sub.2 No Reaction CuS No Reaction CuSO.sub.4 No Reaction CuO
No Reaction Cu(OH).sub.2 5 hours 5.8 No Data No Data *CLA:
Conjugated Linoleic Acid
[0089] Copper compounds as received are shown to be ineffective
hydrogenation catalysts under the conditions described.
Example 2
Reference Hydrogenation Using Copper Chromite
[0090] A commercially available copper chromite catalyst (G22/2 in
powder form from Sud Chemie Inc.) was used without modification.
The hydrogenation reaction was identical to Example 1. The results
given below in Table 2 show that this catalyst produced desirable
levels of linolenic acid with low trans fat content and about 1%
formation of CLA:
TABLE-US-00002 TABLE 2 Final Linolenic Final trans Reaction acid
content fatty acid Final CLA* Catalyst time (%) content (%) content
(%) Copper 5 hours 1.74 7.45 0.96 chromite
Example 3
Hydrogenation Using Copper Powder
[0091] Hydrogenation reactions using commercially available copper
powder (Umicore Canada Inc., product # UCP 500, particle size: 5
microns) were carried out. The results are given in Table 3
below.
No treatment: UPC 500 (12.1 grams) was added without treatment to
598 grams of dry refined and bleached soybean oil. Hydrogenation
conditions were as in Example 1. Treatment 1: UPC 500 (12.0 grams)
was heated in a muffle furnace at 300.degree. C. for several 4-5
minute intervals. After the third interval, the material was
subjected to disrupting the agglomerates or clumps. The
hydrogenation was carried out as in Example 1.
TABLE-US-00003 TABLE 3 Final linolenic acid Copper Reaction C18:0
C18:1 C18:2 content Trans powder time (hr) (%) (%) (%) (%) (%)
Soybean oil 4.3 22.0 52.9 7.2 0.2 No treatment 7 4.3 24.3 51.7 7.0*
0.6 Treatment 1 5 4.3 31.4 49.2 2.4 7.8 *linolenic acid content
estimated from RI (refractive index)
[0092] Copper powder as received ("No treatment" in Table 3) was
ineffective under hydrogenation conditions, and raised the content
of undesirable trans fatty acids without decreasing the linolenic
acid level significantly. After heat treatment including disrupting
any agglomerates and clumps, the catalyst produced an oil with a
decrease of C18:3 with a reasonable increase in trans fatty acids.
As shown in Table 3, the level of C18:1 increased, and the level of
C18:0 was unchanged.
Example 4
Heat-Treated or Hydrogen Peroxide-Treated Copper Carbonate/Copper
Hydroxide
[0093] Hydrogenation reactions using commercially available copper
carbonate/copper hydroxide (basic copper carbonate, CUCOCER,
obtained from World Metals, Inc. and Sigma Aldrich basic copper
carbonate) were carried out. The results are given in Tables 4.1
and 4.2 below.
No treatment: CUCOCER and Sigma Aldrich basic copper carbonate (6
grams) were used as received. Vacuum dried: CUCOCER was vacuum
dried overnight at 350.degree. F. (177.degree. C.) or 500.degree.
F. (260.degree. C.) for 1 hour at 20 mm Hg.
Heat Treatment:
[0094] Treatment 1a: CUCOCER (1.05 grams) was briefly treated at
360.degree. C. in a muffle furnace until the color turned to
avocado green. The hydrogenation reaction was carried out as in
Example 1 using the entire amount as catalyst. Treatment 1b:
CUCOCER (1.05 grams) was treated at 360.degree. C. in a muffle
furnace until the color turned darker than treatment 1a, to
greenish brown (olive drab). The hydrogenation reaction was carried
out as in Example 1 using the entire amount as catalyst. Treatment
1c: CUCOCER (1.05 grams) was heated in a muffle furnace at
300.degree. C. for ten minutes, followed by 350.degree. C. for
about 10 minutes. The catalyst color was black after this
treatment. The hydrogenation reaction was carried out as in Example
1 using the entire amount as catalyst. Treatment 1d: Sigma-Aldrich
basic copper carbonate (25.0 grams) was heated at 350.degree. C.
for four minute intervals, removed from the oven and swirled
briefly to mix, then returned to the muffle furnace for four
minutes of additional heating. When removed from the furnace the
material had it turned black. The hydrogenation reaction was
carried out as in Example 1 using the entire 25 grams as
catalyst.
TABLE-US-00004 TABLE 4.1 Final Trans Linolenic fatty acid Basic
copper Reaction C18:0 C18:1 C18:2 acid content content carbonate
time (%) (%) (%) (%) (%) No treatment 5 hours No reaction CUCOCER
and Sigma Aldrich Vacuum 4 hours No reaction Dried CUCOCER
Treatment 1a 5 hours No reaction Treatment 1b 5 hours 4.2 24.6 51.8
6.9 1.3 Treatment 1c 5 hours 4.3 31.7 48.8 2.5 8.6 Treatment 1d 2
hours No reaction Sigma Aldrich
[0095] The results above show that copper carbonate/copper
hydroxide as received was ineffective as a hydrogenation catalyst.
When CUCOCER was heated at 350.degree. C. so that the powder turned
black (Treatment 1c), an excellent hydrogenation catalyst was
obtained by this process. Oil hydrogenated with this catalyst had
diminished content of linolenic acid and C18:2. Additionally, the
content of C18:1 increased without any noticeable change in
C18:0.
Hydrogen Peroxide Treatment:
[0096] When CUCOCER was contacted with hydrogen peroxide it
darkened to a brown color but did not turn black as when heated at
350.degree. C. Treatment 2a: CUCOCER (4.0 grams) was slurried with
10 ml of 5% hydrogen peroxide for a few minutes. Heat was generated
during the treatment, and the CUCOCER turned an avocado green color
during treatment. The treatment reaction was terminated by
filtering treated CUCOCER through a buchner funnel followed by
washing with deionized water. The chemically treated CUCOCER was
dried in a vacuum desiccator. The hydrogenation reaction was
carried out as in Example 1 using 1.05 g catalyst. Treatment 2b:
CUCOCER (5.4 grams) was slurried with 10 ml of 5% hydrogen peroxide
for a few minutes. Heat was generated during the treatment, and the
CUCOCER turned a dark avocado green color during treatment. The
treatment reaction was terminated by filtering treated CUCOCER
through a buchner funnel followed by washing with deionized water.
The chemically treated CUCOCER was dried in a vacuum desiccator.
The hydrogenation reaction was carried out as in Example 1 using
1.05 g catalyst. Treatment 2c: Sigma Aldrich basic copper carbonate
(24.4 grams) was slurried in 60 ml water. Aliquots (10-15 ml) of a
5% solution of hydrogen peroxide totaling 40 ml were added to the
slurry and the slurry was allowed to incubate for 60 minutes. The
slurry was filtered through a buchner funnel and washed with
deionized water, then dried at room temperature overnight in a
vacuum desiccator. The hydrogenation reaction was carried out as in
Example 1 using 1.05 g catalyst. Treatment 2d: Sigma-Aldrich basic
copper carbonate (20.0 grams) was slurried in water with a total of
10 ml of 50% H.sub.2O.sub.2 added in 2 ml aliquots while the slurry
was held in an ice bath. The product was filtered, washed and dried
in a desiccator as in treatment 2c. The reaction was carried out as
in Example 1 using 1.05 g catalyst except that the reaction was run
at 200.degree. C. Treatment 2e: Treated Sigma-Aldrich-basic copper
carbonate from Treatment 2d (.about.6 grams) was further treated by
placing it in a mortar and slurry grinding with 2 ml of 50%
H.sub.2O.sub.2; this was allowed to be contacted for 30 minutes
while stirring. The catalyst was filtered and dried in a vacuum
desiccator. Hydrogenation was carried out as in Treatment 2d using
1.05 g catalyst.
TABLE-US-00005 TABLE 4.2 Final Trans Linolenic fatty acid Basic
copper Reaction C18:0 C18:1 C18:2 acid content content carbonate
time (%) (%) (%) (%) (%) Treatment 2a 5 hours 4.3 25.3 51.6 6.6 1.9
CUCOCER Treatment 2b* 7 hours 4.3 26.4 51.8 4.3 3.6 CUCOCER
Treatment 2c* 6 hours 4.2 25.7 51.4 5.5 2.5 Sigma Aldrich Treatment
2d 3 hours 4.3 31.3 48.6 2.8 8.1 Sigma-Aldrich Treatment 2e 45 min.
4.3 30.0 49.4 2.8 6.5 Sigma-Aldrich *Fatty acids estimated from
RI
[0097] CUCOCER prepared by Treatment 2a was catalytically active.
CUCOCER treated to a darker color in Treatment 2b was even more
active. The latter yielded a desirable reduction in linolenic acid
without substantially changing the other fatty acid levels.
Hydrogen peroxide treatments were very effective with Sigma Aldrich
basic copper carbonate. Treatment 2c, produced an active catalyst;
however, treatment 2d produced a more active catalyst. Activity was
increased even further in Treatment 2e. The resulting catalyst
produced desirable linolenic acid decrease and increased C18:1
content in a very short reaction time (45 minutes).
Example 5
Hydrogenation Using H.sub.2O.sub.2-Treated Copper Hydroxide
[0098] Hydrogenation reactions using commercially available copper
hydroxide (CUHSULC from World Metals, Inc., also called copper (II)
hydroxide) were carried out. The results are given in Table 5
below.
Hydrogen Peroxide Treatment:
[0099] Treatment 2a: CUHSULC (4.5 grams) was slurried in 10 ml of a
50% solution of hydrogen peroxide. The slurry was filtered on a
Buchner funnel, washed with water and allowed to dry for 48 hours
in a vacuum dissicator. This catalyst (0.96 grams) was added to 600
g oil and the hydrogenation reaction was carried out as in Example
1. Treatment 2b: CUHSULC (5.0 g) was slurried in an ice bath in 10
ml of a 50% solution of hydrogen peroxide, followed by addition of
5 ml of 50% hydrogen peroxide. The slurry was filtered on a Buchner
funnel, washed with water and allowed to dry for 48 hours in a
vacuum dissicator to form an olive drab colored powder. 1.05 Grams
of this CUHSULC catalyst was added to 600 grams of RB soy oil (dry)
and the hydrogenation reaction was carried out as in Example 1.
Treatment 2c: CUHSULC (5.43 grams) was treated with 10 ml 50%
H.sub.2O.sub.2 added dropwise over an ice bath and dried in a
vacuum desiccator. The hydrogenation was done as in Example 1 using
1.05 g catalyst. Treatment 2d: CUHSULC (10.205 g) was slurried in
25 ml water, treated with 10 ml 50% H.sub.2O.sub.2 added dropwise
over an ice bath and dried in a vacuum desiccator. The
hydrogenation was done as in Example 1 using 1.05 g catalyst.
TABLE-US-00006 TABLE 5 Final Final trans Final Copper linolenic
fatty acid CLA hydroxide Reaction C18:0 C18:1 C18:2 acid content
content content treatment time (%) (%) (%) (%) (%) (%) None 5 hours
No reaction 2a 2 hours 4.3 30.5 51.0 1.9 ~7.5 0.7 2b 2 hours 4.2
32.2 49.0 1.69 9.1 0.6 2c 2 hours 4.3 29.9 50.4 2.3 7.3 0.8 2d 1
hour 4.3 29.9 50.0 2.2 7.3 0.8
[0100] Copper (II) hydroxide catalyst prepared by all variations of
treatment 2 were extremely effective hydrogenation catalysts and
rapidly produced an oil with desirable levels of linolenic acid
with low trans fat content and little formation of CLA.
Example 6
Reuse of Copper Hydroxide Catalyst
[0101] CUHSULC (10.21 grams) was treated by first adding 25 ml of
H.sub.2O to effect a slurry, after which 10 ml 50% hydrogen
peroxide was added dropwise to the slurry in an ice bath. The
treated slurry was then filtered, washed and dried in a vacuum
desiccator. The hydrogenation was run using 2.108 grams of catalyst
according to Example 1. The RI of the oil was 1.46151 after 15
minutes and 1.46140 at 30 minutes.
[0102] Second use: the catalyst was recovered by centrifuging the
reaction mixture at 9000 rpm for 15 minutes. No visible catalyst
remained in the oil. The oil was decanted off and fresh oil was
added and used to transfer the catalyst to the reaction vessel in
slurry form with minimal catalyst loss. A total of 600 grams of oil
was used for this reaction and run as in Example 1. The RI after 15
minutes was 1.46131 and after 30 minutes was 1.46121, indicating a
much faster initial hydrogenation than in the first use. This
example demonstrated that the catalyst is recoverable and reusable
with no observable loss of activity on the first reuse. The RI at
one hour was 1.46112.
[0103] Third use: The catalyst was recovered again as for the
second use and reused with 600 g dry RB soy oil as in Example 1.
The reaction was a trace slower than the first reuse, but was still
faster than the initial reaction. The RI after 30 minutes was
1.46132 (which was faster than the original run, 1.46140) and
1.46121 after one hour.
[0104] Fourth use: the catalyst from the third use was recovered as
in the second and third uses and reused a fourth time with 600
grams of dry RB soy oil as in Example 1. The RI after 30 minutes
was 1.46134 and 1.46123 after one hour. The time to reach 2.5%
linolenic acid for this reaction was 2 hours. The results are given
in Table 6 below.
TABLE-US-00007 TABLE 6 Time to attain ~2.5% linolenic Linolenic
Trans Use acid acid (%) (%) 1.sup.st 1 Hour 2.2 7.3 2.sup.nd 1
Hour+ 2.6 7.9 3.sup.rd 1 Hour+ 2.4 8.8 4.sup.th 2 Hours 2.4
9.07
Example 7
Combined Treatments of Copper Hydroxide Catalyst
[0105] Copper hydroxide (5 g) was slurried in 10 ml of a 5%
solution of hydrogen peroxide, followed by addition of 5 ml of 50%
hydrogen peroxide to the slurry in an ice bath. The slurry was
filtered on a Buchner funnel, washed with water and allowed to dry
for 48 hours in a vacuum dissicator to form an olive drab colored
powder. A control reaction was run as in Example 1 with 1.05 grams
of this catalyst. The rest of the copper hydroxide hydrogenation
catalyst was added to 30 ml soybean oil and heated to
160-170.degree. C. with stirring until the catalyst turned black
(about 15 minutes at temperature). The catalyst was recovered by
filtration and used to catalyze hydrogenation reactions as in
example 1 using 1.05 g catalyst at 160.degree. and 180.degree. C.
The results are given in Table 7 below.
TABLE-US-00008 TABLE 7 Final Final trans Copper linolenic fatty
acid hydroxide Reaction C18:0 C18:1 C18:2 acid content content
treatment time (%) (%) (%) (%) (%) Control 2 4.3 29.9 48.6 2.3 7.3
160.degree. C. 160.degree. C. 2 4.3 30.7 50.03 1.9 8.2 180.degree.
C. 1.5 4.3 29.3 50.3 2.6 6.6
[0106] The combination of hydrogen peroxide treatment and heating
in oil in the absence of additional hydrogen provided a hydrogen
peroxide-treated copper hydroxide hydrogenation catalyst with
excellent reduction in linolenic acid content at short reaction
times with little formation of trans fatty acids.
Example 8
Hydrogenation Using Mineral Malachite
[0107] A sample of mineral malachite from Congo, Africa was
obtained from a rock collector. The mineral malachite was ground in
a hand mortar in the laboratory. After grinding the particle size
distribution was: Less than 10 microns, 2.1%; between 10 and 20
microns, 13.3%; greater than 20 microns, 65.5%. The ground mineral
malachite was used at 0.1% (wt. copper/wt. oil) to hydrogenate
dried refined, bleached, deodorized soybean oil at 165.degree. C.
at 60 psig hydrogen for 4 hours. The resulting oil contained 5.39%
C18:0, 37.82% C18:1, 41.48% C18:2, 2.92% C18:3 and 16.23% trans
fatty acids.
Example 9
Hydrogenation Using Precipitated Unsupported Malachite
[0108] Precipitated malachite was prepared by the following
procedures, below and used to catalyze hydrogenation reactions, as
provided below.
[0109] Procedure 1: Unsupported precipitated malachite was prepared
in accordance with the description in H. Parekh and A. Hsu, "The
Preparation of Malachite. Reaction between cupric sulfate and
sodium carbonate solutions." Industrial & Engineering Chemistry
Product Research and Development (1968), 7 (3), 222-6. Commercially
available basic copper carbonate (20.04 grams, World Metal LLC,
Sugar Land, Tex.) was slurried in 140 ml water, and 10.2 ml
concentrated sulfuric acid was added to make a solution of
dissolved copper sulfate. Anhydrous sodium carbonate (24 grams) was
dissolved in 600 ml of water.
[0110] The dissolved copper sulfate solution was added to the
sodium carbonate solution over a five minute period as the sodium
carbonate solution was stirred on a stirring plate. A precipitate
formed and was allowed to settle. About 450 ml of the liquid layer
was removed by decanting and another 200 ml was removed by
siphoning. The precipitate was rinsed with three times with water
(400 ml) to obtain a light green precipitate of malachite, which
was vacuum filtered in a buchner funnel. The precipitated malachite
was then placed in a vacuum oven at 150.degree. C. overnight to
dry.
[0111] The dried precipitated malachite was then used as an
unsupported catalyst without further treatment to catalyze
hydrogenation reactions of refined, bleached, deodorized oil as in
example 1 using 1.04 grams of catalyst. The results are given in
Table 8 below (two different reaction conditions are
illustrated).
[0112] Procedure 2: Unsupported precipitated malachite was prepared
in accordance with the description in H. Parekh and A. Hsu, "The
Preparation of Malachite. Reaction between cupric sulfate and
sodium carbonate solutions." Industrial & Engineering Chemistry
Product Research and Development (1968), 7 (3), 222-6. Commercially
available basic copper carbonate (10.15 grams, World Metal LLC,
Sugar Land, Tex.) was slurried in 50 ml water, and 6.6 ml
concentrated sulfuric acid was added to make a solution of
dissolved copper sulfate. An additional 20 ml of H.sub.2O was added
to resolubilize some of the CuSO.sub.4 which had precipitated out
of the saturated solution. Anhydrous sodium carbonate (12 grains)
was dissolved in 200 ml of water.
[0113] Two-thirds of the dissolved copper sulfate solution was
added dropwise to the sodium carbonate solution as the sodium
carbonate solution was stirred on a stirring plate; the final
one-third was poured in slowly and caused significant effervescing.
A precipitate formed and was allowed to settle. Part of the liquid
layer was removed by decanting and part of the liquid layer was
removed by siphoning. The precipitate was rinsed with three times
with water to obtain a light green precipitate of malachite, which
was vacuum filtered in a buchner funnel. The precipitated malachite
was then placed in a vacuum oven at 150.degree. C. overnight to
dry.
[0114] The dried precipitated malachite was then used as an
unsupported catalyst without further treatment to catalyze
hydrogenation reactions of refined, bleached, deodorized oil as in
example 1 using 1.04 grams of catalyst. The results are given in
Table 8 below.
[0115] Procedure 3: Unsupported precipitated malachite was prepared
in accordance with the description in H. Parekh and A. Hsu, "The
Preparation of Malachite. Reaction between cupric sulfate and
sodium carbonate solutions." Industrial & Engineering Chemistry
Product Research and Development (1968), 7 (3), 222-6. Commercially
available basic copper carbonate (20.04 grams, World Metal LLC,
Sugar Land, Tex.) was slurried in 140 ml water, and 10.2 ml
concentrated H.sub.2SO.sub.4 was added to make a solution of
dissolved copper sulfate. Anhydrous sodium carbonate (24 grams) was
dissolved in 600 ml of water.
[0116] Both solutions were heated to 60.degree. C., and the
dissolved copper sulfate solution was added to the sodium carbonate
solution over a five minute period as the sodium carbonate solution
was stirred on a stirring hot plate. A precipitate formed and was
allowed to settle. About 450 ml of the liquid layer was removed by
decanting and another 200 ml was removed by siphoning. The
precipitate was rinsed with three times with water (400 ml) to
obtain a light green precipitate of malachite, which was vacuum
filtered in a buchner funnel. The precipitated malachite was then
placed in a vacuum oven at 150.degree. C. overnight to dry.
[0117] The dried precipitated malachite was then used as an
unsupported catalyst without further treatment to catalyze
hydrogenation reactions of refined, bleached, deodorized oil as in
example 1 using 1.04 grams of catalyst. The results are given in
Table 8 below.
[0118] Procedure 4: Unsupported precipitated malachite catalyst
prepared by procedure 1 was further treated with hydrogen peroxide
as follows: Unsupported precipitated malachite catalyst (1 gram)
was slurried in water over ice, and 50% hydrogen peroxide (1 ml.)
was added dropwise over a 30 minute period. The slurry was allowed
to warm to room temperature, then and vacuum filtered in a buchner
funnel to provide a chemically treated precipitated malachite
catalyst. The chemically treated precipitated malachite catalyst
was then placed in a vacuum oven at 150.degree. C. overnight to
dry, then used to catalyze hydrogenation reactions of refined,
bleached, deodorized oil as in example 1 using 1.04 grams of
catalyst. The results are given in Table 8 below.
[0119] Commercial basic copper carbonate: Commercial basic copper
carbonate previously purchased from Mallinckrodt Laboratory
Chemicals (Phillipsburg, N.J.) was tested as a catalyst without
further treatment to catalyze hydrogenation reactions of refined,
bleached, deodorized oil as in Example 1 using 0.504 grams of
catalyst. The results are given in Table 8 below.
TABLE-US-00009 TABLE 8 Final Final trans Catalyst Hydrogenation
linolenic fatty acid Expt preparation temperature Reaction C18:0
C18:1 C18:2 acid content content No. procedure (.degree. C.) time
(%) (%) (%) (%) (%) Starting oil 4.3 22.0 52.85 7.5 0.2 1 1 200 3
hrs 4.32 31.18 48.89 2.18 7.38 2 1 160 7 hrs 4.6 28.64 50.45 2.8
5.9 3 2 200 1 hr 4.63 32.92 46.21 1.9 8.7 4 3 160 7 hrs 4.56 30.87
48.55 2.2 8.3 5 4 200 6 hrs 4.32 33.14 47.1 1.94 9.98 6 Commercial
200 30 min 4.20 30.72 48.79 1.82 6.94
[0120] Very good catalysts were obtained with all procedures. The
catalyst prepared by procedure 2 was much faster than catalysts
prepared by other procedures. The Mallinckrodt basic copper
carbonate provided the fastest reaction, with a decrease in
linolenic acid to 1.82% in 30 minutes.
Example 9
Removal of Copper Catalyst from Hydrogenation Reactions
[0121] Hydrogenation of refined bleached soybean oil was carried
out using commercial copper hydroxide (CUHSULC, World Metal, LLC,
Sugarland, Tex.). Catalyst (1.02 grams) was added to soybean oil
(600 grams) and hydrogenation was carried out for seven hours.
Removal of copper from the hydrogenated oil was carried out by
vacuum filtration through a bed (70 mm diameter, 12 mm bed depth)
of Celite 503 Diatomaceous Earth (World Minerals Inc., Goleta,
Calif.) to obtain filtered oil containing 3.47 mg copper per kg
oil. The remaining copper was removed by treating the filtered oil
with a citric acid solution and activated SorbsilR92 (INEOS Silicas
Americas, LLC, Joliet, Ill.;) and filtering through Celite for a
second time. Filtered oil (466 grams) was heated to 80.degree. C.
and 14 drops of 40% citric acid solution was added to the filtered
oil. This mixture was stirred about 15 minutes at 80.degree. C.
Sorbsil R92 (1.86 grams) was added and stirred for about 30
minutes. The mixture was again vacuum filtered through a bed of
Celite 503 as described above to obtain treated oil free from
copper (detection limit: 0.1 mg/kg).
Example 10
Ratios of Fatty Acids
[0122] Ratios of fatty acids in a) starting soybean oil, and b) oil
obtained after hydrogenating soybean oil according to the methods
above (referenced below by Table No.) were calculated and are given
below in Table 9.
TABLE-US-00010 TABLE 9 C18:2/ C18:2C/ Linolenic/ Description #
C18:0 18:1 C18:0 Starting oil 12.09 2.18 1.81 Table 2 Copper
chromite 15 10.94 1.85 0.53 Table 2 Copper chromite 16 12.05 1.87
0.86 Table 3 Copper powder No treat. 17 12.02 2.13 1.63 Table 3
Copper powder Treat. 1 18 11.44 1.57 0.56 Table 4.1 Treat. 1b World
Metals 19 12.33 2.11 1.64 Table 4.1 Treat. 1c World Metals 20 11.35
1.54 0.58 Table 4.2 Treat. 2a World Metals 21 12.00 2.04 1.53 Table
4.2 Treat. 2b World Metals 22 12.05 1.96 1.00 Table 4.2 Treat. 2c
Sigma Aldrich 23 12.24 2.00 1.31 Table 4.2 Treat. 2d Sigma-Aldrich
24 11.30 1.55 0.65 Table 4.2 Treat. 2e Sigma-Aldrich 25 11.49 1.65
0.65 Table 5 2a 26 11.86 1.67 0.44 Table 5 2b 27 11.67 1.52 0.40
Table 5 2c 28 11.72 1.69 0.53 Table 5 2d 29 11.63 1.67 0.51 Table 7
Control 30 11.30 1.63 0.53 Table 7 160.degree. C. 31 11.63 1.63
0.44 Table 7 180.degree. C. 32 11.70 1.72 0.60 Example 8 Mineral
malachite 33 7.70 1.10 3.01 Table 8 Expt. 1 34 11.32 1.57 0.50
Table 8 Expt. 2 35 10.97 1.76 0.61 Table 8 Expt. 3 36 9.98 1.40
0.41 Table 8 Expt. 4 37 10.65 1.57 0.48 Table 8 Expt. 5 38 10.90
1.42 0.45 Table 8 Expt. 6 39 11.62 1.59 0.43
[0123] Desired fatty acid profiles include those with reduced
content of linolenic acid without higher levels of trans fatty
acids compared to the starting oil. It is also highly desirable to
carry out this reaction without reducing the content of C18:2 or
C18:1 fatty acids, or increasing the content of C18:0 fatty
acids.
[0124] Illustratively, vegetable oils that are hydrogenated using
the processes according to the present invention can be comprised
of fatty acid chains having one of the following profiles:
[0125] C18:2/C18:0 ratio above about 11.0; C18:2/C18:1 ratio no
greater than about 2.2; C18:3/18:0 ratio no greater than about
1.7;
[0126] C18:2/18:0 above about 11.3; C18:2/C18:1 no greater than
about 1.65; C18:3/18:0 no greater than about 0.65;
[0127] C18:2/18:0 above about 9.95; C18:2/C18:1 no greater than
about 1.80; C18:3/18:0 no greater than about 0.65; and
[0128] C18:2/18:0 above about 11.3; C18:2/C18:1 no greater than
about 1.70; C18:3/18:0 no greater than about 0.65.
[0129] Having now fully described this invention, it will be
understood to those of ordinary skill in the art that the same can
be performed within a wide and equivalent range of conditions,
formulations, and other parameters without affecting the scope of
the invention or any embodiment thereof.
[0130] All documents, e.g., scientific publications, patents,
patent applications and patent publications, if cited herein are
hereby incorporated by reference in their entirety to the same
extent as if each individual document was specifically and
individually indicated to be incorporated by reference in its
entirety. Where the document cited only provides the first page of
the document, the entire document is intended, including the
remaining pages of the document.
* * * * *